【作者】 张旭茗；

【导师】 李莉；

【作者基本信息】 哈尔滨工程大学 ， 材料学， 2013， 博士

【摘要】 由于海洋生物污损能够带来的巨大损失，防污涂层的研究一直是人们研究的热点。尤其是随着人们环保意识的提高，以及对海洋生物污损过程的深入了解，对于新型仿生防污涂层要求越来越多，进而开发了具有微相分离结构的仿生防污涂层。研究表明，具有微相分离结构的表面可以防止蛋白吸附，进而可以用来进行海洋生物防污。由于具有微相分离结构的共聚物体系较少，这种防污涂层尚处于研究阶段，对防污涂层制备技术和防污机理研究也不足。本文的基本思想是选用几种常见并且比较廉价的聚合物为链段模型，设计出不同体系的共聚物，并采用模拟方法预测各种共聚物涂层的微相分离结构；同时，利用化学方法合成所设计的共聚物，并对其进行微相分离结构以及防污性能研究。首先，本文选用几种常见廉价并且对海洋环境没有污染的共聚物为链段，分别设计了PDMS/PS嵌段共聚物、PMMA/PS随机共聚物及PMMA/PEG接枝共聚物，并利用耗散粒子动力学方法，对不同成分含量的三种共聚物分别进行了涂层表面微相分离结构的预测。对PDMS含量分别为10%、20%~90%的PDMS/PS嵌段共聚物涂层，PMMA含量分别为10%、20%~90%的PMMA/PS随机共聚物涂层，以及PMMA含量分别为10%、20%~50%的PMMA/PEG接枝共聚物涂层的微相分离结构预测结果均表明，随着共聚物中某一成分含量的增加，共聚物涂层的微相分离结构呈现从这一成分的颗粒状，到岛状，到双连续状，再到另一成分的岛状，颗粒状的变化规律。其次，根据所预测的涂层表面的微相分离结构，经过多次试验，制定了合理的化学合成工艺，并选用合适的原料成功地合成了PDMS含量分别为32%、41%和50%的PDMS/PS嵌段共聚物，PMMA含量分别为19%、62%、69%和84%的PMMA/PS随机共聚物，以及PEG含量分别为8%、10%和12%的PMMA/PEG接枝共聚物，并利用FT-IR、1H-NMR、UV和DSC等方法对所合成的共聚物进行了表征。同时利用旋转涂膜方法对各共聚物表面进行成膜，并利用轻敲模式AFM方法观察了涂层表面的形貌。结果表明，三种共聚物涂层表面的微相分离结构均与所预测的表面结构一致，均是以相对亲水的相为凸起的分散相，相对疏水的相为连续相形式分布，并且随着共聚物中相对亲水成分含量的增加，凸起的相区的尺寸有所增加。再次，对于所制备的共聚物涂层分别进行了润湿性和防污性能的研究。PDMS/PS、PMMA/PS及PMMA/PEG三种共聚物涂层的接触角测量的结果表明，共聚物涂层的润湿性主要取决于涂层的组成；其中PDMS/PS涂层的疏水性最强，PMMA/PS涂层次之，而PMMA/PEG具有亲水性；并且在每种共聚物涂层中，疏水性均随着疏水性强的链段的增加而增加。通过牛血清蛋白吸附试验及小新月菱形藻吸附试验，对PDMS/PS、PMMA/PS及PMMA/PEG三种共聚物涂层的防污性能的研究。结果表明，尽管三种共聚物涂层具有不同的表面疏水性及微相分离尺寸，但三种共聚物涂层均具有良好的防蛋白和藻类吸附的性能，并且防污性能相当。研究结果说明了三种涂层的防污性能不仅与涂层的亲疏水性有关，而且很大程度上取决于涂层表面的结构。最后，为深入研究共聚物涂层中微相分离结构与防污性能之间的关系，本文根据所测试的共聚物涂层的防污性能，从吸附物尺寸小于和大于材料表面微相分离结构两个角度，系统的研究了共聚物涂层的防污机理。揭示了本文中的三种共聚物表面结构与防污性能的关系，为其它具有微相分离结构材料的防污机理研究提供了依据。更多还原

【Abstract】 The settlement of microorganisms as marine biofouling, has enormous harm upon shipsand other sea facilities. Playing an increasingly important role in marine organisms atifouling.Antifouling coatings become a hotspot of research interests nowadays. Antifouling coatingswith microphase separation structure were developed, with the improvement of people’sconsciousness of environment protection and the deeply understanding of marine foulingorganism mechanism. It is identified that the surfaces of coatings with microphase separationstructure have function in preventing the adsorption of proteins, thus they can be used inmarine pollution prevention. The basic thinking of the research is selecting some common andcheap polymers as chain segments to design a series of copolymers. At the same time, thesurface structures of the copolymers will be predicted. After that the copolymers will besynthesized and the surface structure and properties will be studied.Firstly, a series of common, cheap and no pollution to the marine environment polymerswere chosen as chain segments, and PDMS/PS block copolymer, PMMA/PS randomcopolymer and PMMA/PEG graft copolymer were designed respectively. Meanwhile, thesurface microphase structures of the copolymers with different components were forecastedby DPD method. The predicting results of PDMS/PS copolymer coatings with10%,20%~90%PDMS contents, PMMA/PS copolymer coatings with10%,20%~90%PMMAcontents, and PMMA/PEG copolymer coatings with10%,20%~90%PEG contents showedthat, with the increase of one segment in copolymers, the structure of the coatings changedfrom particle form to island form of one phase, then to bicontinuous structure, then to islandform and particle form of the other phase.Secondly, according to the prediction for the surface structure of the copolymers coatings,reasonable chemical synthesis processes were made. And PDMS/PS copolymers with32%,41%and50%PDMS contents, PMMA/PS copolymers with19%,62%,69%and84%PMMA contents and PMMA/PEG copolymers with8%,10%and12%PEG contents weresynthesized respectively. The copolymers were characterized by FT-IR,1H-NM, UV and DSCmethod. Copolymer coatings were prepared by spin-casting method, and surface structure of the coatings were studied by tapping mode AFM. It was showed that the surface structures ofthe coatings were consistent with the predictions. Thereinto the relatively hydrophilic phasewere dispersed phase, and relatibely hydrophobic phase were continuous phase. With theincrease of dispersed phase in copolymer coatings, the phase size increased.Thirdly, wettability and antifouling performance of copolymer coatings were studied.Water contact angle experiment was used to study the surface wettability of PDMS/PS,PMMA/PS and PMMA/PEG copolymers coatings. The results showed that the wettabiltiy ofthe coatings depended on the components of copolymers. The antifouling propertiesPDMS/PS, PMMA/PS and PMMA/PEG copolymer coatings were studied by bovine serumalbumin adsorption experiment and nitzschia closterium minutissima adsorption experiment.The results showed that the antifouling properties of copolymer coatings depent not only onthe wettability but also on the surface structure.Lastly, for further study of the relationship between the structures and antifoulingperformance, antifouling mechanism was studied from adsorption content size was less thanand more than the phase separation structure points of view. The antifouling performances ofthe copolymer coating in this paper were revealed by that mechanism, furthermore, thismechanism provided theory basis for other materials with micro phase separation structure inexplaining the antifouling performance.更多还原